Urea of the anthraquinone series and process of making same.



. UNITED STATES PATENT OFFICE.

ALBRECHT scnmm AND GEORG KRANZLEIN, or HUCHST-ON -THE-MAIN, QERMANY,

ASSIGNORS TO FARBVVERKE vomu. MEISTER. LUCIUS & BRUNING, or HOGHST-ON- THE-MAIN, GERMANY, A CORPORATION OF GERMANY.

UREA OF THE ANTHRAQUINONE SERIES AND PROCESS OF MAKING SAME.

No Drawing.

specification of Letters Patent.

Application filed October 27, 1909. Serial 110. 524,853.

Patented. May 17', 19).

(A.NH.CO.NH.R)

have not, been disclosed hitherto, neither ose of the alpha series nor those of the beta series.

Vij'e'have now found that the anthraquiiionylnreas of the beta series, that is to say urea derivatives for instance of the type \.N11.oc.Nn.1-: in which stands for a residue of beta-anthraquinonyl and R for an aromatic residue such anthraquinonyl, anthraquinonyl urea and the like-can be obtained by treating the betaanthra uinonyl derivatives of the type ANTI. C.RIin which *Rl stands for a residue such'as alcoxyl, aroxyl, chlorin, etc.that is to say beta-anthraquin0nyl compounds, for instance beta-anthraquinonyl urethane, beta-anthraquinonyl urea chlorid, with such ainins as for instance amidoanthraquinones, d an:idoanthraquinones, etc. Thus for instance the sym metrical neta-beta-dianthraapiinonyl urea (beta) A.NH.CO.NH.A. (beta), i. c. an urea of the type beta A.I\ lI.CO.XH.1l.in which R also stands for a residue of beta nnthraquinonyl,-can be produced by heating a bcta-anthraquinohyl urethane, for in stance (beta) A..\'ll.C0.0(. .Il or for instance a corres ending beta-anthraquinonyl urea chlorid eta) AlZILOtLCl with the respective beta-ainidoanthraquinoac. in this manner for instance by heatin, the beta-anthraquinony] urethane with betaamidoantlu'aquinone, a yellow substance is produced winch is insoluble in alkali and which must be regarded as beta-beta-dianthraquinon l urea. The same substance is obtained y heating with beta-amidoanthraquinone the urea chlorid which, for instance, is obtained by introducing an excess of phosgene into a cold suspension of beta-umidoanthraquinone :u nitrobenzene. Thus also the unsymmetrical areas whichcontrary to what is the case with the symmetrical beta-beta-dianthraquinonyl urea,

do not contain the same residue of betaantbraqninonyl, can be obtained b heating the beta-anthraquinonyl urea ch orid ti less promptly b heating the beta-anthrzn u nonyl ur thane; with such amins as alphaamidoant iraquiuone, dimnidoanthraqninones etc. These beta-anthraquinonyl urea derivatives are to be used as parent materials i'or other valuable dyestuffs and are themselves vat dyestuffs of great value.

Example I: 30 kg. of beta-anthraqub nonyl urethane, obtained from beta-amideanthraquinone and ethyl-chloro carbonatc, are mixed with 22.5 kg. of betaamidoanthrarpiinone and immediately heated for a short time to about 250". The resulting yellow product of the reaction is purified by means of nitrobcnzene. The substance thus obtained is insoluble in acids and alkalics; when combined with an alkaline solution of hydrosulfite it forms a reddishbrown rat from which particularly cotton, but. also wool, are dyed yellow tints. It has the constitution For preparing larger quantities, it is advantageous to add a neutral solvent with a high boiling point, such as for instance naphthal nc, for the purpose of better equalizing the temperature. If, instead of the abovementioned urethane, the product obtainable by the reaction of an excessmf pliosgcne on lnrta-amidoonthraquiuonc nitrobe'nzezm in the cold!(debt-anthraquinonyl urea chlorid) is used as parent-material and heated with bcta-an1ideanthraquinonc, an analogous result is obtained. The procedure for reducing the beta-anthraquinone urea ch orid is as follows: An excess of phosgcnc is intr'o- 100 duced into a suspension of 22.3 parts by weigh. of beta-antidoanthraqninone in about 200 parts of nit-robenzene in the cold; this mixture is stirred until the orange yellow color of the beta-amidoanthraquinone has 105 turn d to a grayish-white colorunduntil the nydro hlorid of botaannidoanthraqui none has gradually disafppeared. The re-. sulting paste is filtered 0 and washeclwitn benzene; after removing the benzenefll'ic' BEST Avmizm co y chlorid obtained is mixed with 23.3 parts of beta-antidoanth aquinone and heated with nitrobenzene or with another solvent, or with or without the addition of an allialine substance. The product is the same as regards its properties as the product above described.

As thebeta-anthraquinonyl urea chlorid when combined with water partly breaks up into beta-amidoanthraquinone, carbon (llOXld and hydrochloric acid, the diant-hrauinonyl urea is also formed according to tie reaction above referred to, by heating the beta-anthraquinonyl urea chlorid alone with a little quantity of water or with alkalies and water, for instance by heating it in technical hydrous nitrobenzene, although in the latter case it, is contaminated with bet. amidoanthraquinones.

In the last-mentioned manner considerable quantitiesi of beta beta dianthraquinonyl urea are, for instance, obtained bv heating the above-mentioned suspension of bct -anthraquinonyl urea chlorid in technical undried nitrobenzcne; thus by heating grams of beta-anthraquinonyl urea chlorid in 1000 grams of technical, perfectly clear but not particularly dried, nitrobcnzene and then filtering oft the resulting product hot, 28.5 grams of bcta-bcta-dianthraqninonyl urea, i. a. about 757; of the theoretical quantity, are obtained. The same yield is obtained by heating the bet-aan t h raquinonyl urea chlorid to 100 with three times its uantity of water and purifying the resu ting product with nitrobcnzcne; thus, for instance, from 12? grams of urea chlorid 79 grams ot beta-bcta-dianthraquinonyl urea are obtained. that is to say about 77% of the theoretical quantity. 1

If the beta-anthraquinonyl urea chlorid is replaced by beta bcta-anthraquinonymne diurea chlorid, obtainable by the reaction of an excess of phosgeuc on beta-beta-diamidoanthraquinonc, and the latter is heated with alpha-aniitloanthraqninone (:2 molecules), :1

urea deriva ive dyeing in the vat gold-yel-.

low tints is obtained. the procedure bein" as follows: 18:. kgr. of 2.6 anthraquinony ene dim-ea chlorid, obtainable, like the betaanthraqniaonyl urea chlorid, by the action of pho gene on a suspension of 2.6 diamidoanthraqninone in nitrobenze-ne, are "redually heated to ebullition with 22.3 fig. of alpha-amidoanthraquinone in 400 kg. of absolutely dry nitrobenzeue, while stirrin After some hours the mass is allowed-to cool. is then filtered. off, washed with alcohol and dried. The yellow dyestutl" thus produced dissolves in concentrated sulfuric acid with an oran e-rcd color and dyes from the altar line by i'osulfite vat cotton rich gold-yellow tints of great fastne s.

' It alphu-amid a ithraoninomis subs-ii;

tuted for betaamidoauthraq'ii; me. w. :1

beta-anthraquinonyl urea chlorid (one ioleride) is heated with alpha-amidoantln'aqui-- non-:2, a reaction-product obtained dyeing in the Vat yellowish tints of a greenish hue; the same substance may also be produced by heating the beta-anthraquinonyl urethane with alpha-amidoanthraqninone. but in this case it is much less pure and intermixed with other substances of unknown compo ition. It alpha-alphadiamidoanthraquinon-a is substituted for alphaamidoanthraqninone, 2'. e. if beta-anthraqninonyl urea Chit rid (2 molecules) are heated with an alphaalpha -diainidoanthraquinone, brcwn vat dyestuffs are obtained, the procedure being as shown by the following example: 11.05 kg. of 1.5 diamidoanthraquinone and 400 kg of nitrobenzene are heated to ebullition and then 23.6 kg. of beta-anthraquinonyl urea chlorid are introduced while stirring. After having been boiled for several hours the mass is allowed to cool, is then filtered off, washed with alcohol and dried. The brown powder thus obtained didsolves in alkaline hydrosulfitc with a reddish-brown color and dyes from this-solution wool and cotton reddish-brown tints of excellent qualities as regards fastness. If instead of the 1.5 diamidoanthraquinone the 1.4 or 1.3

diamidoanthraquinone is used, brown dycstaffs of great value are obtained in an analogous manner. The nrca-derivatiw produced from 1.4-diainidoanthraquin -n:- and beta-anthraquinouyl urea chlorid (t: molecules) dyes from the alkaline hydro sultite vat cotton brown ints, while the tri anthraquinonyl urea produced from 1.1- diainidoanthraquinone dyes cotton yello. ish-brown tints of a somewhatfaintcr tin-r than those obtainable from 1.5 dianlidoanthraquinonc. It, in the foregoing ex"- ample, for the 1.5 diamidqanthraquinom; 2.6-diamid0authraqninone is substituted, an

anthraqninonyl urea is obtained which dyes cotton in the vat fast yellow tints.

For dyeing purposes the procedure may for instance be as follows: One part by weight of the dycstutl' btainable from beta-- authraquinonyl urethane and beta-amideanthraquinone, or from beta-anthraquincnyl urea chlorid and beta aniiiloanthraquinone, is mixed and stirred with 50 parts of water and 2 parts of caustic soda lye of 40 B. to this are added I} parts of concentrated hydrosulfite powder and the whole is heated to 30-50 C. until it forms a solution. This mother-vat is introduced into the dye-- vat containing 500 arts of water and 10 arts of Glaubcr an t, then the cotton is ycd in this vat f r half an hour in the cold, squeezed and allowed to oxidize in the air. Thus a, fast bright yellow tint is obtaine. The procedure for dyeing wool is similar, exc pt that this material is dyed in fainter am? s -aw v'liat duller-tints. 

